Azeotropic compositions comprising fluorinated compounds for cleaning applications

ABSTRACT

The present invention relates to compositions comprising fluorinated olefins or fluorinated ketones, and at least one alcohol, halocarbon, hydrofluorocarbon, or fluoroether and combinations thereof. In one embodiment, these compositions are azeotropic or azeotrope-like. In another embodiment, these compositions are useful in cleaning applications as a degreasing agent or defluxing agent for removing oils and/or other residues from a surface.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application is a divisional of pending U.S. application Ser. No.11/712,453, filed Feb. 28, 2007, which claims the benefit of priority ofU.S. Provisional Application 60/777,350, filed Feb. 28, 2006.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions comprising fluorinatedolefins, or fluorinated ketones, and at least one alcohol, halocarbon,fluoroalkyl ether, or hydrofluorocarbon and combinations thereof. Thesecompositions are azeotropic or azeotrope-like and are useful in cleaningapplications as a defluxing agent and for removing oils or residues froma surface.

2. Description of Related Art

Flux residues are always present on microelectronics componentsassembled using rosin flux. As modern electronic circuit boards evolvetoward increased circuit and component densities, thorough boardcleaning after soldering becomes a critical processing step. Aftersoldering, the flux-residues are often removed with an organic solvent.De-fluxing solvents should be non-flammable, have low toxicity and havehigh solvency power, so that the flux and flux-residues can be removedwithout damaging the substrate being cleaned. Further, other types ofresidue, such as oils and greases, must be effectively removed fromthese devices for optimal performance in use.

Alternative, non-ozone depleting solvents have become available sincethe elimination of nearly all previous CFCs and HCFCs as a result of theMontreal Protocol. While boiling point, flammability and solvent powercharacteristics can often be adjusted by preparing solvent mixtures,these mixtures are often unsatisfactory because they fractionate to anundesirable degree during use. Such solvent mixtures also fractionateduring solvent distillation, which makes it virtually impossible torecover a solvent mixture of the original composition.

Azeotropic solvent mixtures may possess the properties needed for thesede-fluxing, de-greasing applications and other cleaning agent needs.Azeotropic mixtures exhibit either a maximum or a minimum boiling pointand do not fractionate on boiling. The inherent invariance ofcomposition under boiling conditions insures that the ratios of theindividual components of the mixture will not change during use and thatsolvency properties will remain constant as well.

The present invention provides azeotropic and azeotrope-likecompositions useful in semiconductor chip and circuit board cleaning,defluxing, and degreasing processes. The present compositions arenon-flammable, and as they do not fractionate, will not produceflammable compositions during use. Additionally, the used azeotropicsolvent mixtures may be re-distilled and re-used without compositionchange.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to compositions comprising fluorinatedolefins and, at least one compound selected from the group consisting ofalcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons andcombinations thereof. In one embodiment, the at least one compound isselected from the group consisting of:

n-propylbromide;

trichloroethylene;

tetrachloroethylene;

trans-1,2-dichloroethylene;

methanol;

ethanol;

n-propanol;

isopropanol;

C₄F₉OCH₃;

C₄F₉OC₂H₅;

HFC-43-10mee;

HFC-365mfc

and combinations thereof.

In one embodiment, the compositions are azeotropic or azeotrope-like.Additionally, the present invention relates to processes for cleaningsurfaces and for removing residue from surfaces, such as integratedcircuit devices.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate by reference the entire contents ofall cited references in this disclosure. Further, when an amount,concentration, or other value or parameter is given as either a range,preferred range, or a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of any upper range limit or preferredvalue and any lower range limit or preferred value, regardless ofwhether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

In one embodiment, the present invention relates to compositionscomprising compounds having the formula E- or Z—R¹CH═CHR² (Formula I),wherein R¹ and R² are, independently, C1 to C5 perfluoroalkyl groups,and at least one alcohol, halocarbon, fluoroalkyl ethers, orhydrofluorocarbon and combinations thereof. Examples of R¹ and R² groupsinclude, but are not limited to, CF₃, C₂F₅, n-C₃F₇, i-C₃F₇, n-C₄F₉,n-C₅F₁₁, and i-C₄F₉. Exemplary, non-limiting Formula I compounds arepresented in Table 1.

TABLE 1 Code Structure IUPAC Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluoro-2-butene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoro-2-pentene F13E CF₃CH═CH(n-C₃F₇)1,1,1,4,4,5,5,6,6,6-decafluoro-2- hexene F13iE CF₃CH═CH(i-C₃F₇)1,1,1,4,4,5,5,5-heptafluoro-4- (trifluoromethyl)-2-pentene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluoro-3- hexene F14ECF₃CH═CH(n-C₄F₉) 1,1,1,4,4,5,5,6,6,7,7,7- dodecafluorohept-2-ene F23EC₂F₅CH═CH(n-C₃F₇) 1,1,1,2,2,5,5,6,6,7,7,7- dodecafluorohept-3-ene F23iEC₂F₅CH═CH(i-C₃F₇) 1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15E CF₃CH═CH(n-C₅F₁₁)1,1,1,4,4,5,5,6,6,7,7,8,8,8- tetraddecafluorooct-2-ene F24EC₂F₅CH═CH(n-C₄F₉) 1,1,1,2,2,5,5,6,6,7,7,8,8,8- tetradecafluorooct-3-eneF3i3iE i-C₃F₇CH═CH(i-C₃F₇) 1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trimethylfluoro)hex-3-ene F33iE n-C₃F₇CH═CH(i-C₃F₇)1,1,1,2,5,5,6,6,7,7,7-undecafluoro- 2(trifluoromethyl)hept-3-ene F34En-C₃F₇CH═CH(n-C₄F₉) 1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F3i4E i-C₃F₇CH═CH(n-C₄F₉)1,1,1,2,5,5,6,6,7,7,8,8,8- triskaidecafluoro-2(trifluoromethyl)oct-3-ene F44E n-C₄F₉CH═CH(n-C₄F₉)1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10, 10-octadecafluorodec-5-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include those fabricated fromstainless steels, in particular of the austenitic type, and thewell-known high nickel alloys such as Monel® nickel-copper alloys,Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et. al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Temperatures for contacting of said perfluoroalkyl iodide with saidperfluoroalkyltrihydroolefin are preferably within the range of about150° C. to 300° C., more preferably from about 170° C. to about 250° C.,and most preferably from about 180° C. to about 230° C. Pressures forcontacting of said perfluoroalkyl iodide with saidperfluoroalkyltrihydroolefin are preferably the autogenous pressure ofthe reactants at the reaction temperature.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distillation prior to the dehydroiodination step.

In yet another embodiment, the contacting of a perfluoroalkyliodide witha perfluoroalkyltrihydroolefin takes place in the presence of acatalyst. In one embodiment, a suitable catalyst is a Group VIIItransition metal complex. Representative Group VIII transition metalcomplexes include, without limitation, zero valent NiL₄ complexes,wherein the ligand, L, can be a phosphine ligand, a phosphite ligand, acarbonyl ligand, an isonitrile ligand, an alkene ligand, or acombination thereof. In one such embodiment, the Ni(0)L₄ complex is aNiL₂(CO)₂ complex. In one particular embodiment, the Group VIIItransition metal complex is bis(triphenyl phospine)nickel(0) dicarbonyl.In one embodiment, the ratio of perfluoroalkyl iodide toperfluoroalkyltrihydroolefin is between about 3:1 to about 8:1. In oneembodiment, the temperature for contacting of said perfluoroalkyl iodidewith said perfluoroalkyltrihydroolefin in the presence of a catalyst, iswithin the range of about 80° C. to about 130° C. In another embodiment,the temperature is from about 90° C. to about 120° C.

In one embodiment, the contact time for the reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin in thepresence of a catalyst is from about 0.5 hour to about 18 hours. Inanother embodiment, the contact time is from about 4 to about 12 hours.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent depends on the solubility of the basic substance, thesolubility of the perfluoroalkyl iodide, and the solubility of theperfluoroalkyltrihydroolefin as well as the boiling point of theproduct, and the ease of separation of traces of the solvent from theproduct during purification. Typically, ethanol or isopropanol are goodsolvents for the reaction. Separation of solvent from the product may beeffected by distillation, extraction, phase separation, or a combinationof the three.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction vessel may be fabricated from glass,ceramic, or metal and is preferably agitated with an impellor or otherstirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, ethylene dichloride, chloroform, carbontetrachloride, or perchloroethylene), or ether (e.g., diethyl ether,methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran,dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of aphase transfer catalyst. Suitable phase transfer catalysts includequaternary ammonium halides (e.g., tetrabutylammonium bromide,tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride,dodecyltrimethylammonium chloride, and tricaprylylmethylammoniumchloride), quaternary phosphonium halides (e.g.,triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride),cyclic ether compounds known in the art as crown ethers (e.g.,18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to one ormore solid or liquid basic substance(s).

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation, optionally after addition ofwater, by distillation, or by a combination thereof.

In another embodiment, the invention relates to compositions comprisingperfluoroethyl isopropyl ketone(1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone, (PEIK)and at least two compounds selected from the group consisting ofalcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons. PEIKhas CAS Reg. No. 756-13-8) and is available from 3M™ (St. Paul, Minn.).

In yet another embodiment, the invention relates to compositionscomprising nonafluoro-1-hexene (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene),(PFBE), and at least one compound selected from the group consisting ofalcohols, halocarbons, fluoralkyl ethers, and hydrofluorocarbons andcombinations thereof. 3,3,4,4,5,5,6,6,6-Nonafluoro-1-hexene, also knownas HFC-1549fz, has CAS Registry Number 19430-93-4 and is available fromE.I. DuPont de Nemours & Co (Wilmington, Del.).

In yet another embodiment, the invention relates to a process forcleaning surfaces using azeotropic or azeotrope-like compositionscomprising a fluorinated olefin, or a fluorinated ketone and at leastone compound selected from the group consisting of alcohols,halocarbons, fluoroalkyl ethers, and hydrofluorocarbons.

The fluorolefins of Table 1, PEIK, and PFBE may be combined with thecompounds listed in Table 2 to form the present inventive compositions.The at least one compound selected from the group consisting ofalcohols, halocarbons, fluoroalkyl ethers, or hydrofluorocarbons to becombined with PFBE shall not be an alcohol, trans-1,2-dichloroethylenealone, C₄F₉OCH₃ alone, HFC-43-10mee alone, HFC-365mfc alone, or amixture of trans-1,2-dichloroethylene and C₄F₉OC₂H₅.

TABLE 2 Synonym (or CAS registry Name Chemical formula abbreviation)number Halocarbons trichloroethylene CHCl═CCl₂ TCE 79-01-6tetrachloroethylene CCl₂═CCl₂ PCE 127-18-4 (or perchloroethylene)n-propylbromide CH₃CH₂CH₂Br nPBr trans-1,2- CHCl═CHCl t-DCE 156-60-5dichloroethylene Alcohols methanol CH₃OH MeOH 67-56-1 ethanol CH₃CH₂OHEtOH 64-17-5 n-propanol CH₃CH₂CH₂OH n-PrOH 71-23-8 isopropanolCH₃CH(OH)CH₃ IPA 67-63-0 Fluoroethers mixture of isomers-CF₃CF₂CF₂CF₂OCH₃ C₄F₉OCH₃ 163702-07-6 1,1,1,2,2,3,3,4,4- and andnonafluoro-4- (CF₃)₂CFCF₂OCH₃ 163702-08-7 methoxybutane and 2-(methoxy-difluoromethyl)- 1,1,1,2,3,3,3- heptafluoropropane mixture of isomers-CF₃CF₂CF₂CF₂OC₂H₅ C₄F₉OC₂H₅ 163702-05-4 1-ethoxy- and and1,1,2,2,3,3,4,4,4- (CF₃)₂CFCF₂OC₂H₅ 163702-06-5 nonafluorobutane and2-(ethoxy- difluoromethyl)- 1,1,1,2,3,3,3- heptafluoropropaneHydrofluorocarbons 1,1,1,2,3,4,4,5,5,5- CF₃CHFCHFCF₂CF₃ HFC-43-decafluoropentane 10mee 1,1,1,3,3- CF₃CH₂CF₂CH₃ HFC-365mfcpentafluorobutane

The compounds listed in Table 2 are commercially available from chemicalsupply houses. C₄F₉OCH₃, and C₄F₉OC₂H₅ are available from 3M™ (St. Paul,Minn.). HFC-43-10mee is available from E.I. DuPont de Nemours & Co(Wilmington, Del.). HFC-365mfc is available from Solvay-Solexis.

The compositions of the present invention may be prepared by anyconvenient method by combining the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combining the components in an appropriate vessel.Agitation may be used, if desired.

The compositions of the present invention comprise compositionscontaining one of the fluoroolefins listed in Table 1, PEIK, or PFBE,and at least one of the compounds selected from the group consisting of:trichloroethylene; tetrachloroethylene; trans-1,2-dichloroethylene;n-propylbromide; methanol; ethanol; n-propanol; isopropanol; C₄F₉OCH₃;C₄F₉OC₂H₅; HFC-43-10mee; HFC-365mfc; and combinations thereof. In oneembodiment, the compositions are azeotropic or azeotrope-like. Theexception thereto being that according to the compositions of thepresent invention, PFBE is not combined with an alcohol,trans-1,2-dichloroethylene alone, C₄F₉OCH₃ alone, HFC-43-10mee alone,HFC-365mfc alone, or a mixture of trans-1,2-dichloroethylene orC₄F₉OC₂H₅.

As used herein, an azeotropic composition is a constant boiling liquidadmixture of two or more substances wherein the admixture distillswithout substantial composition change and behaves as a constant boilingcomposition. Constant boiling compositions, which are characterized asazeotropic, exhibit either a maximum or a minimum boiling point, ascompared with that of the non-azeotropic mixtures of the samesubstances. Azeotropic compositions as used herein include homogeneousazeotropes which are liquid admixtures of two or more substances thatbehave as a single substance, in that the vapor, produced by partialevaporation or distillation of the liquid, has the same composition asthe liquid. Azeotropic compositions as used herein also includeheterogeneous azeotropes where the liquid phase splits into two or moreliquid phases. In these embodiments, at the azeotropic point, the vaporphase is in equilibrium with two liquid phases and all three phases havedifferent compositions. If the two equilibrium liquid phases of aheterogeneous azeotrope are combined and the composition of the overallliquid phase calculated, this would be identical to the composition ofthe vapor phase.

As used herein, the term “azeotrope-like composition” also sometimesreferred to as “near azeotropic composition,” means a constant boiling,or substantially constant boiling liquid admixture of two or moresubstances that behaves as a single substance. One way to characterizean azeotrope-like composition is that the vapor produced by partialevaporation or distillation of the liquid has substantially the samecomposition as the liquid from which it was evaporated or distilled.That is, the admixture distills/refluxes without substantial compositionchange. Another way to characterize an azeotrope-like composition isthat the bubble point vapor pressure of the composition and the dewpoint vapor pressure of the composition at a particular temperature aresubstantially the same. Herein, a composition is azeotrope-like if,after 50 weight percent of the composition is removed such as byevaporation or boiling off, the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed by evaporation orboil off is less than 10 percent.

In cleaning apparati, such as vapor degreasers or defluxers, some lossof the cleaning compositions may occur during operation through leaks inshaft seals, hose connections, soldered joints and broken lines. Inaddition, the working composition may be released to the atmosphereduring maintenance procedures on equipment. If the composition is not apure compound or azeotropic or azeotrope-like composition, thecomposition may change when leaked or discharged to the atmosphere fromthe equipment, which may cause the composition remaining in theequipment to become flammable or to exhibit unacceptable performance.Accordingly, it is desirable to use as a cleaning composition a singlefluorinated hydrocarbon or an azeotropic or azeotrope-like compositionthat fractionates to a negligible degree upon leak or boil-off.

The azeotropic compositions of one embodiment of the present inventionare listed in Table 3.

TABLE 3 Comp A Comp B wt % A wt % B T (C.) F14E methanol 85.1 14.9 59.1F14E isopropanol 87.1 12.9 66.9 F14E ethanol 87.9 12.1 65.2 F14E t-DCE44.3 55.7 44.0 F14E nPBr 54.4 45.6 66.6 F24E methanol 72.1 27.9 63.4F24E isopropanol 78.1 21.9 74.1 F24E ethanol 79.2 20.8 71.8 F24E t-DCE24.5 75.5 45 F24E nPBr 25.7 74.3 70.2 F24E PCE 85.2 14.8 89.9 F24E TCE65.0 35.0 75.9 PEIK methanol 97.0 3.0 43.5 PEIK isopropanol 96.7 3.345.5 PEIK ethanol 96.8 3.2 44.7 PEIK t-DCE 72.9 27.1 34.7 PEIK 43-10mee73.2 26.8 47.7 PEIK 365mfc 38.8 61.2 38.1 PFBE methanol 92.2 7.8 50.6PFBE isopropanol 95.2 4.8 56.3 PFBE ethanol 94.8 5.2 55.2 PFBE t-DCE52.8 47.2 41.3 PFBE nPBr 82.3 17.7 57.1 F22E methanol 95.8 4.2 43.7 F22Eisopropanol 98.0 2.0 47.2 F22E ethanol 97.6 2.4 46.6 F22E t-DCE 71.029.0 33.9 F22E nPBr 87.0 13.0 43.3 F22E 43-10mee 89.8 10.2 47.9 F22E365mfc 29.3 70.7 39.2 F13iE methanol 95.5 4.5 44.4 F13iE isopropanol97.8 2.2 48.0 F13iE ethanol 97.4 2.6 47.5 F13iE t-DCE 70.2 29.8 34.4F13iE nPBr 86.4 13.6 44.0 F13iE 43-10mee 95.3 4.7 48.8 F13iE 365mfc 24.675.4 39.5 F3i3iE methanol 85.0 15.0 59.8 F3i3iE isopropanol 89.2 10.870.0 F3i3iE ethanol 89.0 11.0 67.8 F3i3iE t-DCE 44.1 55.9 44.5 F3i3iEC₄F₉OC₂H₅ 22.8 77.2 75.7 F3i3iE nPBr 67.4 32.6 61.3 F13E methanol 94.45.6 47.3 F13E isopropanol 96.9 3.1 51.9 F13E ethanol 96.5 3.5 51.1 F13Et-DCE 66.3 33.7 36.3 F13E nPBr 83.7 16.3 47.1 F13E 43-10mee 59.5 40.552.3 F3i4E t-DCE 7.6 92.4 47.6 F3i4E methanol 42.8 57.2 65.4 F3i4Eisopropanol 57.8 42.2 81.0 F3i4E ethanol 58.7 41.3 77.3 F3i4E nPBr 31.968.1 69.6 F44E nPBr 8.1 91.9 70.9

Additionally in another embodiment, the azeotropic compositions of thepresent invention may include ternary and quarternary azeotropiccompositions comprising compounds from Table 2. Examples withoutlimitation of these higher order azeotropic compositions are exemplifiedin Table 4 along with the atmospheric pressure boiling points for thecompositions.

TABLE 4 Comp A Comp B Comp C wt % A wt % B wt % C T (C.) F14E t-DCEmethanol 34.4 59.0 6.6 39.9 F14E t-DCE ethanol 41.9 55.1 3.0 43.2 F24Et-DCE methanol 10.3 80.3 9.4 41.0 F24E t-DCE ethanol 24.8 70.9 4.3 43.0PEIK t-DCE methanol 71.5 26.4 2.1 33.0 PEIK t-DCE ethanol 73.0 25.7 1.334.2 PEIK t-DCE 43-10mee 57.0 26.9 16.1 34.3 PEIK t-DCE 365mfc 43.7 24.132.2 32.6 PFBE t-DCE C₄F₉OCH₃ 40.1 47.5 12.4 41.3 F22E t-DCE methanol67.9 29.7 2.4 32.6 F22E t-DCE 365mfc 45.4 27.2 27.4 33.0 F13iE t-DCEmethanol 66.9 30.6 2.5 33.0 F13iE t-DCE 43-10mee 69.8 29.8 0.4 34.4F13iE t-DCE 365mfc 41.9 27.8 30.3 33.3 F3i3iE t-DCE methanol 32.9 60.26.9 40.1 F3i3iE t-DCE ethanol 41.1 56.3 2.6 43.8 F13E t-DCE methanol62.2 34.7 3.1 34.5 F13E t-DCE 43-10mee 48.0 33.2 18.8 36.1 F13E t-DCE365mfc 23.1 30.3 46.6 34.4

The binary azeotrope-like compositions of the present invention arelisted in Table 5.

TABLE 5 Comp A Comp B wt % A wt % B T (C.) F14E Methanol 60-99  1-4059.1 F14E Isopropanol 70-99  1-30 66.9 F14E Ethanol 72-99  1-28 65.2F14E t-DCE 1-75 25-99  44.0 F14E nPBr 1-99 1-99 66.6 F14E C₄F₉OCH₃ 1-991-99 50 F14E C₄F₉OC₂H₅ 1-99 1-99 50 F14E 43-10mee 1-99 1-99 50 F24EMethanol 1-91 9-99 63.4 F24E Isopropanol 57-91  9-43 74.1 F24E Ethanol57-92  8-43 71.8 F24E t-DCE 1-63 37-99  46.1 F24E nPBr 1-70 30-99  70.2F24E PCE 61-99  1-39 89.9 F24E TCE 40-84  16-60  75.9 F24E C₄F₉OC₂H₅1-99 1-99 50 PEIK Methanol 91-99  1-9  43.5 PEIK Isopropanol 57-99  1-1645.5 PEIK Ethanol 85-99  1-15 44.7 PEIK t-DCE 50-88  12-50  34.7 PEIK4310mcee 1-99 1-99 47.7 PEIK 365mfc 1-99 1-99 38.1 PEIK C₄F₉OCH₃ 1-991-99 50 PFBE Methanol 80-99  1-20 50.6 PFBE Isopropanol 83-99  1-17 56.3PFBE Ethanol 83-99  1-17 55.2 PFBE t-DCE 21-79  21-79  41.3 PFBE nPBr44-99  1-55 57.1 PFBE C₄F₉OCH₃ 1-99 1-99 50 PFBE C₄F₉OC₂H₅ 1-99 1-99 50PFBE 43-10mee 1-99 1-99 50 PFBE 365mfc 1-99 1-99 50 F22E Methanol 86-99 1-14 43.7 F22E Isopropanol 88-99  1-12 47.2 F22E Ethanol 88-99  1-1246.6 F22E t-DCE 48-87  13-52  33.9 F22E nPBr 64-99  1-36 43.3 F22E43-10mee 1-99 1-99 47.9 F22E 365mfc 1-99 1-99 39.2 F22E C₄F₉OCH₃ 1-991-99 50 F13iE Methanol 86-99  1-14 44.4 F13iE Isopropanol 87-99  1-1348.0 F13iE Ethanol 88-99  1-12 47.5 F13iE t-DCE 46-86  14-54  34.4 F13iEnPBr 64-99  1-36 44.0 F13iE 43-10mee 1-99 1-99 48.8 F13iE 365mfc 1-991-99 39.5 F13iE C₄F₉OCH₃ 1-99 1-99 50 F3i3iE Methanol 57-99  1-43 59.8F3i3iE Isopropanol 73-99  1-27 70.0 F3i3iE Ethanol 73-99  1-27 67.8F3i3iE t-DCE 1-76 24-99  44.5 F3i3iE C₄F₉OC₂H₅ 1-99 1-99 75.7 F3i3iEnPBr 43-86  14-57  61.3 F3i3iE C₄F₉OCH₃ 1-99 1-99 50 F13E Methanol84-99  1-16 47.3 F13E Isopropanol 86-99  1-14 51.9 F13E Ethanol 86-99 1-14 51.1 F13E t-DCE 42-84  16-58  36.3 F13E nPBr 61-99  1-39 47.1 F13E43-10mee 1-99 1-99 52.3 F13E C₄F₉OCH₃ 1-99 1-99 50 F13E C₄F₉OC₂H₅ 1-991-99 50 F13E 365mfc 1-99 1-99 50 F3i4E t-DCE 1-69 31-99  47.6 F3i4EMethanol 1-89 11-99  65.4 F3i4E Isopropanol 1-88 12-99  81 F3i4E Ethanol1-89 11-99  77.3 F3i4E nPBr 1-72 28-99  69.6 F44E nPBr 1-70 30-99  70.9

In addition to the binary azeotrope-like compositions in the precedingtable, higher order (ternary or quarternary) azeotrope-like compositionsare included in the present invention. Examples without limitation ofternary or higher order azeotrope-like compositions are given in Table6.

TABLE 6 Comp A Comp B Comp C wt % A wt % B wt % C T (C.) F14E t-DCEC₄F₉OCH₃ 1-70 20-70 1-70 50 F14E t-DCE C₄F₉OC₂H₅ 1-70 29-90 1-60 50 F14Et-DCE 43-10mee 1-80 15-60 1-80 50 F14E t-DCE 365mfc 1-70 10-60 1-80 50F14E t-DCE Methanol 1-70 29-98 1-30 39.9 F14E t-DCE ethanol 1-70 29-981-20 43.2 F24E t-DCE C₄F₉OCH₃ 1-70 20-70 1-70 50 F24E t-DCE C₄F₉OC₂H₅1-60 30-80 1-60 50 F24E t-DCE Methanol 1-50 40-98 1-25 41.0 F24E t-DCEethanol 1-60 39-98 1-20 45.0 PEIK t-DCE C₄F₉OCH₃ 1-70 20-50 1-70 50 PEIKt-DCE Methanol 50-85  14-49 1-9  33.0 PEIK t-DCE ethanol 50-85  14-491-9  34.2 PEIK t-DCE 43-10mee 1-85 10-65 1-80 34.3 PEIK t-DCE 365mfc1-85  1-55 1-85 32.6 PFBE t-DCE 43-10mee 1-70 20-60 1-79 50 PFBE t-DCE365mfc 1-70 15-60 1-80 50 PFBE t-DCE C₄F₉OCH₃ 1-75 24-75 1-70 41.3 F22Et-DCE C₄F₉OCH₃ 1-70 29-70 1-70 50 F22E t-DCE 43-10mee 1-80 19-60 1-80 50F22E t-DCE Methanol 45-85  14-54 1-10 32.6 F22E t-DCE 365mfc 1-89 10-601-85 33.0 F13iE t-DCE C₄F₉OCH₃ 1-75 24-70 1-70 50 F13iE t-DCE Methanol45-85  14-54 1-10 33.0 F13iE t-DCE 43-10mee 1-89 10-60 1-80 34.4 F13iEt-DCE 365mfc 1-89 10-60 1-84 33.3 F3i3iE t-DCE Methanol 1-70 29-95 1-2540.1 F3i3iE t-DCE ethanol 1-65 34-98 1-15 43.8 F3i3iE t-DCE C₄F₉OCH₃1-69 30-70 1-69 50 F3i3iE t-DCE C₄F₉OC₂H₅ 1-69 30-80 1-69 50 F13E t-DCEMethanol 45-80  19-54 1-10 34.5 F13E t-DCE 43-10mee 1-85 14-60 1-80 36.1F13E t-DCE 365mfc 1-85 14-60 1-80 34.4 F13E t-DCE C₄F₉OCH₃ 1-80 19-701-70 50 F3i4E t-DCE C₄F₉OCH₃ 1-30 25-69 30-69  50 F3i4E t-DCE C₄F₉OC₂H₅1-50 30-98 1-60 50 F44E t-DCE C₄F₉OC₂H₅ 1-70  1-60 29-98  50

In yet another embodiment of the invention, the compositions of thepresent invention may further comprise an aerosol propellant. Aerosolpropellants may assist in delivering the present compositions from astorage container to a surface in the form of an aerosol. Aerosolpropellant is optionally included in the present compositions in up to25 weight percent of the total composition. Representative aerosolpropellants comprise air, nitrogen, carbon dioxide, difluoromethane(HFC-32, CH₂F₂), trifluoromethane (HFC-23, CHF₃), difluoroethane(HFC-152a, CHF₂CH₃), trifluoroethane (HFC-143a, CH₃CF₃; or HFC-143,CHF₂CH₂F), tetrafluoroethane (HFC-134a, CF₃CH₂F; HFC-134, CHF₂CHF₂),pentafluoroethane (HFC-125, CF₃CHF₂), heptafluoropropane (HFC-227ea,CF₃CHFCF₃), pentafluoropropane (HFC-245fa, CF₃CH₂CHF₂), dimethyl ether(CH₃OCH₃), or mixtures thereof.

In an embodiment of the invention, the present inventive azeotropiccompositions are effective cleaning agents, defluxers and degreasers. Inparticular, the present inventive azeotropic compositions are usefulwhen de-fluxing circuit boards with components such as Flip chip, μBGA(ball grid array), and Chip scale or other advanced high-densitypackaging components. Flip chips, μBGA, and Chip scale are terms thatdescribe high density packaging components used in the semi-conductorindustry and are well understood by those working in the field.

In another embodiment the present invention relates to a process forremoving residue from a surface or substrate, comprising: contacting thesurface or substrate with a composition of the present invention andrecovering the surface or substrate from the composition.

In a process embodiment of the invention, the surface or substrate maybe an integrated circuit device, in which case, the residue comprisesrosin flux or oil. The integrated circuit device may be a circuit boardwith various types of components, such as Flip chips, μBGAs, or Chipscale packaging components. The surface or substrate may additionally bea metal surface such as stainless steel. The rosin flux may be any typecommonly used in the soldering of integrated circuit devices, includingbut not limited to RMA (rosin mildly activated), RA (rosin activated),WS (water soluble), and OA (organic acid). Oil residues include but arenot limited to mineral oils, motor oils, and silicone oils.

In the inventive process, the means for contacting the surface orsubstrate is not critical and may be accomplished by immersion of thedevice in a bath containing the composition, spraying the device withthe composition or wiping the device with a substrate that has been wetwith the composition. Alternatively, the composition may also be used ina vapor degreasing or defluxing apparatus designed for such residueremoval. Such vapor degreasing or defluxing equipment is available fromvarious suppliers such as Forward Technology (a subsidiary of the CrestGroup, Trenton, N.J.), Trek Industries (Azusa, Calif.), and Ultronix,Inc. (Hatfield, Pa.) among others.

An effective composition for removing residue from a surface would beone that had a Kauri-Butanol value (Kb) of at least about 10, preferablyabout 40, and even more preferably about 100. The Kauri-Butanol value(Kb) for a given composition reflects the ability of said composition tosolubilize various organic residues (e.g., machine and conventionalrefrigeration lubricants). The Kb value may be determined by ASTMD-1133-94.

The following specific examples are meant to merely illustrate theinvention, and are not meant to be limiting in any way whatsoever.

EXAMPLES Example 1 Synthesis of1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene (F14E) Synthesis ofC₄F₉CH₂CHICF₃

Perfluoro-n-butyliodide (180.1 gm, 0.52 moles) and3,3,3-trifluoropropene (25.0 gm, 0.26 moles) were added to a 400 mlHastelloy™ shaker tube and heated to 200° C. for 8 hours underautogenous pressure which increased to a maximum of 428 PSI. Aftercooling the reaction vessel to room temperature, the product wascollected. The product of this reaction and two others carried out insubstantially the same manner, except that one of the reactions hadtwice the quantity of reactants, were combined and distilled to give322.4 gm of C₄F₉CH₂CHICF₃ (52.2° C./35 mm, 70% yield).

Conversion of C₉F₉CH₂CHICF₃ to F14E

A 2 liter round bottom flask equipped with a stirring bar and packeddistillation column and still head was charged with isopropyl alcohol(95 ml), KOH (303.7 gm, 0.54 moles) and water (303 ml). C₄F₉CH₂CHICF₃(322.4 gm, 0.73 mole) was added dropwise via addition funnel to theaqueous KOH/IPA mixture at room temperature. The reaction was thenheated to 65-70° C. to recover the product by distillation, Thedistillated was collected, washed with sodium metabisulfite and water,dried over MgSO₄ and then distilled through a 6-inch (15.2 cm) columnpacked with glass helices. The product, F14E (173.4 gm, 76% yield),boils at 78.2° C. It was characterized by NMR spectroscopy (¹⁹F: δ-66.7(CF₃, m, 3F), −81.7 (CF₃, m, 3F), −124.8 (CF₂, m, 2F), −126.4 (CF₂, m,2F), −114.9 ppm (CF₂, m, 2F); ¹H, 6.58d)

Example 2 Synthesis of1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene (F24E) Synthesis ofC₄F₉CHICH₂C₂F₅

Perfluoroethyliodide (220 gm, 0.895 mole) and3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene (123 gm, 0.50 mole) were added toa 400 ml Hastelloy™ shaker tube and heated to 200° C. for 10 hours underautogenous pressure. The product from this and two others carried outunder substantially similar conditions were combined and washed with two200 mL portions of 10 wt % aqueous sodium bisulfite. The organic phasewas dried over calcium chloride and then distilled to give 277.4 gm ofC₄F₉CH₂CHICF₃ (79-81° C./67-68 mm Hg) in 37% yield.

Conversion of C₄F₉CHICH₂C₂F₅ to F24E

A 1 L round bottom flask equipped with a mechanical stirrer, additionfunnel, condenser, and thermocouple was charged with C₄F₉CHICH₂C₂F₅(277.4 gm, 0.56 moles) and isopropanol (217.8 g). The addition funnelwas charged with a solution of potassium hydroxide (74.5 g, 1.13 moles)dissolved in 83.8 g of water. The KOH solution was added dropwise to theflask with rapid stirring over the course of about one hour as thetemperature slowly increased from 21° C. to 42° C. The reaction mass wasdiluted with water and the product recovered by phase separation. Theproduct was washed with 50 mL portions of 10 wt % aqueous sodiumbisulfite and water, dried over calcium chloride, and then distilled atatmospheric pressure. The product, F24E (128.7 gm, 63%) boils at 95.5°C. and was characterized by NMR (¹⁹F: δ-81.6 (CF₃, m, 3F), −85.4 (CF₃, m3F), −114.7 (CF₂, m, 2F), −118.1 (CF₂, m, 2F), −124.8 ppm (CF₂, m, 2F),−126.3 ppm (CF₂, m, 2F); ¹H: δ6.48; chloroform-d solution).

Example 3 Synthesis of1,1,1,4,5,5,5-Heptafluoro-4-(trifluoromethyl)-pent-2-ene (F13iE)Synthesis of CF₃CHICH₂CF(CF₃)₂

(CF₃)₂CFI (265 gm, 0.9 moles) and 3,3,3-trifluoropropene (44.0 gm, 0.45moles) were added to a 400 ml Hastelloy™ shaker tube and heated to 200°C. for 8 hours under autogenous pressure which increased to a maximum of585 psi. The product was collected at room temperature to give 110 gm of(CF₃)₂CFCH₂CHICF₃ (76-77° C./200 mm) in 62% yield.

Conversion of (CF₃)₂CFCH₂CHICF₃ to F13iE

A 500 ml round bottom flask equipped with a stirring bar and connectedto a short path distillation column and dry ice trap was charged withisopropyl alcohol (50 ml), KOH (109 gm, 1.96 moles) and water (109 ml).The mixture was heated to 42° C. and (CF₃)₂CFCH₂CHICF₃ (109 gm, 0.28moles) was added dropwise via an addition funnel. During the addition,the temperature increased from 42 to 55° C. After refluxing for 30minutes, the temperature in the flask increased to 62° C. and theproduct was collected by distillation. The product was collected, washedwith water, dried with MgSO₄, and distilled. The product, F13iE (41 gm,55% yield), boils at 48-50° C. and was characterized by NMR (19F:δ-187.6 (CF, m 1F), −77.1 (CF3, m 6F), −66.3 (CF3, m 3F); chloroform-dsolution).

Example 4 Synthesis of C4F9CHICH2C2F5

3,3,4,4,5,5,6,6,6-Nonafluorohex-1-ene (20.5 gm, 0.0833 mole),bis(triphenyl phosphine)nickel(0) dicarbonyl (0.53 g, 0.0008 mole), andperfluoroethyliodide (153.6 gm, 0.625 mole) were added to a 210 mlHastelloy™ shaker tube and heated at 100° C. for 8 hours underautogenous pressure. Analysis of the product by GC-MS indicated thepresence of C4F9CHICH2C2F5 (64.3 GC area %) and the diadduct (3.3 GCarea %); the conversion of 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene was80.1%.

Example 5 De-Fluxing

The compositions of the present invention are effective for cleaningionic contamination (flux residue) from a surface. The test used todetermine surface cleanliness involved the following steps:

-   1. A rosin flux was painted liberally onto a FR-4 test board (an    epoxy printed wiring board with tracing made of tinned copper).-   2. The board so treated was then heated in an oven at about 175° C.    for about 1-2 minutes to activate the rosin flux.-   3. The board was then immersed in solder (Sn63, a 63/37 Sn/lead    solder) at about 200° C. for about 10 seconds.-   4. The board was then cleaned by immersion in the boiling cleaning    composition for about 3 minutes and providing gentle movement of the    board. The board was then immersed in a fresh, room temperature bath    of cleaning composition to rinse for about 2 minutes.-   5. The board was then tested for residual ionics with an Omega Meter    600 SMD ionic analyzer.

The cleaning performance was determined by weighing the board prior todeposition of the flux, after the deposition of the flux and then afterthe cleaning procedure. The results are given in Table 7.

TABLE 7 Composition Dry weight Wet weight Post dry weight % (wt %)(grams) (grams) (grams) soil removed PEIK/t- 5.4951 5.5689 5.5010 92%DCE/MeOH 5.0578 5.1401 5.0613 96% (71.5/26.4/ 5.4815 5.5554 5.4846 96%2.1) 3.3450 5.4124 5.3483 95% Average 95%

Example 6 Metal Cleaning

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. The tare weight of each coupon was determined to 0.1mg. A small amount of mineral oil was applied with a swab, the couponwas then re-weighed to obtain the “loaded” weight. The coupon was thencleaned by immersion into a boiling cleaning composition for 1 minute,held in vapor for 30 seconds and then air dried for 1 minute. The couponwas then re-weighed and the percent of soil removed calculated using the3 recorded weights. The results are shown in Table 8.

TABLE 8 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed PEIK/t-DCE 21.588 21.6238 21.5881100 (72.9/27.1) 21.5882 21.62.17 21.5877 101 21.2181 21.3160 21.2180 100Average 100

The results show efficient removal of mineral oil residue from stainlesssteel surfaces by the compositions of the present invention.

Example 7 Metal Cleaning

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. The tare weight of each coupon was determined to 0.1mg. A small amount of DC 200 Silicone was applied with a swab, thecoupon was then re-weighed to obtain the “loaded” weight. The coupon wasthen cleaned by immersion into a boiling cleaning composition for 1minute, held in vapor for 30 seconds and then air dried for 1 minute.The coupon was then weighed and the percent of soil removed iscalculated using the 3 recorded weights. The results are shown in Table9.

TABLE 9 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed PEIK/t-DCE 21.2183 21.2634321.2183 100 (72.9/27.1) 19.0196 19.0461 19.0198 99 21.3960 21.448021.3963 99 Average 100

The results show efficient removal of silicone residue from stainlesssteel surfaces by the compositions of the present invention.

Example 8 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. Each coupon was weighed to 4 places to obtain a tareweight. A small amount of mineral oil was applied with a swab, thecoupon is then weighed to obtain the “loaded” weight. The coupon wasthen cleaned by immersion into a boiling cleaning composition for 1minute, held in vapor for 30 seconds and then air dried for 1 minute.The coupon was then weighed and the percent of soil removed iscalculated using the 3 recorded weights. The results are shown in Table10.

TABLE 10 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed PEIK/MeOH 21.2968 21.3525 21.302989 (97.0/3.0) 21.2470 21.62678 21.2530 71 21.5313 21.5656 21.5417 70Average 77

The results show efficient removal of mineral oil residue from stainlesssteel surfaces by the compositions of the present invention.

Example 9 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. Each coupon was weighed to 4 places to obtain a tareweight. A small amount of DC 200 Silicone was applied with a swab, thecoupon is then weighed to obtain the “loaded” weight. The coupon wasthen cleaned by immersion into a boiling cleaning composition for 1minute, held in vapor for 30 seconds and then air dried for 1 minute.The coupon was then weighed and the percent of soil removed iscalculated using the 3 recorded weights. The results are shown in Table11.

TABLE 11 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed PEIK/MeOH 20.9536 20.9902 20.9536100 (97.0/3.0) 21.1531 21.1889 21.1528 101 20.6276 20.6735 20.6285 98Average 100

Example 10 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. Each coupon was weighed to 4 places to obtain a tareweight. A small amount of mineral oil was applied with a swab, thecoupon is then weighed to obtain the “loaded” weight. The coupon wasthen cleaned by immersion into a boiling cleaning composition for 1minute, held in vapor for 30 seconds and then air dried for 1 minute.The coupon was then weighed and the percent of soil removed iscalculated using the 3 recorded weights. The results are shown in Table12.

TABLE 12 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed F24E/t-DCE 21.6977 21.739621.6972 101 (24.2/75.8) 19.0213 19.0848 19.0207 101 21.2883 21.312721.2874 104 21.5190 21.5599 21.5183 102 21.5046 21.5438 21.5036 103Average 102

Example 11 Metal Cleaning Efficacy

Stainless steel (type 316) 2″×3″ coupons that have been grit blasted toprovide an unpolished surface were pre-cleaned and oven dried to removeany residual soil. Each coupon was weighed to 4 places to obtain a tareweight. A small amount of DC 200 Silicone oil was applied with a swab,the coupon is then weighed to obtain the “loaded” weight. The coupon wasthen cleaned by immersion into a boiling cleaning composition for 1minute, held in vapor for 30 seconds and then air dried for 1 minute.The coupon was then weighed and the percent of soil removed iscalculated using the 3 recorded weights. The results are shown in Table13.

TABLE 13 Post Dry Composition Dry weight Wet weight weight Percent Soil(wt %) (grams) (grams) (grams) removed F24E/t-DCE 21.6973 21.817 21.733370 (24.2/75.8) 19.0203 19.1243 19.0263 94 21.5040 21.5912 21.5193 8221.5183 21.5977 21.5230 94 21.2873 21.3495 21.2909 94 Average 87

The results show efficient removal of silicone residue from stainlesssteel surfaces by the compositions of the present invention.

Example 12

A mixture of 21.8% F24E and 78.2% 1,2-trans-dichloroethylene (t-DCE) byweight was prepared and placed into a 5-plate distillation apparatus,with a 10:1 reflux ratio. The temperature at the distillation head wasrecorded and several cuts of the distilled material were removed overtime. Distilled material was analyzed by gas chromatography. Data isshown in table 14 below. Composition and temperature remained stablethroughout the experiment, indicating azeotropic behavior of thismixture.

TABLE 14 Distillation cut Head temp (C.) Wt % distilled % F24E % t-DCE 145 8 24.5 75.6 2 45 15 24.3 75.7 3 45 22 24.2 75.8 4 45 28 24.2 75.8

Example 13

A mixture of 20.0% F24E, 75.8% 1,2-trans-dichloroethylene (t-DCE) and4.2% ethanol by weight was prepared and placed into a 5-platedistillation apparatus, with a 10:1 reflux ratio. The temperature at thedistillation head was recorded and several cuts of the distilledmaterial were removed over time. Distilled material was analyzed by gaschromatography. Data is shown in table 15 below. Composition andtemperature remained stable throughout the experiment, indicatingazeotropic behavior of this mixture.

TABLE 15 Head temp Wt % Distillation cut (C.) distilled % F24E % t-DCE %EtOH 1 43 13 24.8 71.0 4.3 2 43 19 25.3 70.4 4.3 3 43 25 24.8 70.8 4.3 443 32 24.8 70.9 4.3 5 43 40 24.9 70.8 4.3 6 43 47 24.8 70.9 4.3

1. (canceled)
 2. (canceled)
 3. (canceled)
 4. (canceled)
 5. (canceled) 6.(canceled)
 7. (canceled)
 8. (canceled)
 9. (canceled)
 10. (canceled) 11.(canceled)
 12. An azeotropic or azeotrope-like composition consistingessentially of an azeotropic or azeotrope-like composition selected fromthe group consisting of: about 60 to about 99 weight percent F14E andabout 1 to about 40 weight percent methanol; about 70 to about 99 weightpercent F14E and about 1 to about 30 weight percent isopropanol; about72 to about 99 weight percent F14E and about 1 to about 28 weightpercent ethanol; about 1 to about 75 weight percent F14E and about 25 toabout 99 weight percent trans-1,2-dichloroethylene; about 1 to about 99weight percent F14E and about 99 to about 1 weight percentn-propylbromide; about 1 to about 99 weight percent F14E and about 99 toabout 1 weight percent C₄F₉OCH₃; about 1 to about 99 weight percent F14Eand about 99 to about 1 weight percent C₄F₉OC₂H₅; about 1 to about 99weight percent F14E and about 99 to about 1 weight percent HFC43-10mee;about 1 to about 91 weight percent F24E and about 99 to about 9 weightpercent methanol; about 57 to about 91 weight percent F24E and about 43to about 9 weight percent isopropanol; about 57 to about 92 weightpercent F24E and about 43 to about 8 weight percent ethanol; about 1 toabout 70 weight percent F24E and about 99 to about 30 weight percentn-propylbromide; about 61 to about 99 weight percent F24E and about 39to about 1 weight percent perchloroethylene; about 40 to about 84 weightpercent F24E and about 60 to about 16 weight percent trichloroethylene;about 1 to about 99 weight percent F24E and about 99 to about 1 weightpercent C₄F₉OC₂H₅; about 86 to about 99 weight percent F22E and about 14to about 1 weight percent methanol; about 88 to about 99 weight percentF22E and about 12 to about 1 weight percent isopropanol; about 88 toabout 99 weight percent F22E and about 12 to about 1 weight percentethanol; about 48 to about 87 weight percent F22E and about 52 to about13 weight percent trans-1,2-dichloroethylene; about 64 to about 99weight percent F22E and about 36 to about 1 weight percentn-propylbromide; about 1 to about 99 weight percent F22E and about 99 toabout 1 weight percent HFC-43-10mee; about 1 to about 99 weight percentF22E and about 99 to about 1 weight percent HFC-365mfc; about 1 to about99 weight percent F22E and about 99 to about 1 weight percent C₄F₉OCH₃;about 86 to about 99 weight percent F13iE and about 14 to about 1 weightpercent methanol; about 87 to about 99 weight percent F13iE and about 13to about 1 weight percent isopropanol; about 88 to about 99 weightpercent F13iE and about 12 to about 1 weight percent ethanol; about 46to about 86 weight percent F13iE and about 54 to about 14 weight percenttrans-1,2-dichloroethylene; about 64 to about 99 weight percent F13iEand about 36 to about 1 weight percent n-propylbromide; about 1 to about99 weight percent F13iE and about 99 to about 1 weight percentHFC-43-10mee; about 1 to about 99 weight percent F13iE and about 99 toabout 1 weight percent HFC-365mfc; about 1 to about 99 weight percentF13iE and about 99 to about 1 weight percent C₄F₉OCH₃; about 57 to about99 weight percent F3i3iE and about 43 to about 1 weight percentmethanol; about 73 to about 99 weight percent F3i3iE and about 27 toabout 1 weight percent isopropanol; about 73 to about 99 weight percentF3i3iE and about 27 to about 1 weight percent ethanol; about 1 to about76 weight percent F3i3iE and about 99 to about 24 weight percenttrans-1,2-dichloroethylene; about 1 to about 99 weight percent F3i3iEand about 99 to about 1 weight percent C₄F₉OC₂H₅; about 43 to about 86weight percent F3i3iE and about 57 to about 14 weight percentn-propylbromide; about 1 to about 99 weight percent F3i3iE and about 99to about 1 weight percent C₄F₉OCH₃; about 84 to about 99 weight percentF13E and about 16 to about 1 weight percent methanol; about 86 to about99 weight percent F13E and about 14 to about 1 weight percentisopropanol; about 86 to about 99 weight percent F13E and about 14 toabout 1 weight percent ethanol; about 42 to about 84 weight percent F13Eand about 58 to about 16 weight percent trans-1,2-dichloroethylene;about 61 to about 99 weight percent F13E and about 39 to about 1 weightpercent n-propylbromide; about 1 to about 99 weight percent F13E andabout 99 to about 1 weight percent HFC-43-10mee; about 1 to about 99weight percent F13E and about 99 to about 1 weight percent C₄F₉OCH₃;about 1 to about 99 weight percent F13E and about 99 to about 1 weightpercent C₄F₉OC₂H₅; about 1 to about 99 weight percent F13E and about 99to about 1 weight percent HFC365mfc; about 1 to about 69 weight percentF3i4E and about 99 to about 31 weight percenttrans-1,2-dichloroethylene; about 1 to about 89 weight percent F3i4E andabout 99 to about 11 weight percent methanol; about 1 to about 88 weightpercent F3i4E and about 99 to about 12 weight percent isopropanol; about1 to about 89 weight percent F3i4E and about 99 to about 11 weightpercent ethanol; about 1 to about 72 weight percent F3i4E and about 99to about 28 weight percent n-propylbromide; about 1 to about 70 weightpercent F44E and about 99 to about 30 weight percent n-propylbromide;about 1 to about 70 weight percent F14E, about 29 to about 98 weightpercent trans-1,2-dichloroethylene, and about 1 to about 30 weightpercent methanol; about 1 to about 70 weight percent F14E, about 29 toabout 98 weight percent trans-1,2-dichloroethylene, and about 1 to about20 weight percent ethanol; about 1 to about 70 weight percent F14E,about 20 to about 70 weight percent trans-1,2-dichloroethylene, andabout 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 70 weightpercent F14E, about 29 to about 90 weight percenttrans-1,2-dichloroethylene, and about 1 to about 60 weight percentC₄F₉OC₂H₅; about 1 to about 80 weight percent F14E, about 15 to about 60weight percent trans-1,2-dichloroethylene, and about 1 to about 80weight percent HFC-43-10mee; about 1 to about 70 weight percent F14E,about 10 to about 60 weight percent trans-1,2-dichloroethylene, andabout 1 to about 80 weight percent HFC-365mfc; about 1 to about 50weight percent F24E, about 40 to about 98 weight percenttrans-1,2-dichloroethylene, and about 1 to about 25 weight percentmethanol; about 1 to about 60 weight percent F24E, about 39 to about 98weight percent trans-1,2-dichloroethylene, and about 1 to about 20weight percent ethanol; about 1 to about 70 weight percent F24E, about20 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 toabout 70 weight percent C₄F₉OCH₃; about 1 to about 60 weight percentF24E, about 30 to about 80 weight percent trans-1,2-dichloroethylene,and about 1 to about 60 weight percent C₄F₉OC₂H₅; about 45 to about 85weight percent F22E, about 14 to about 54 weight percenttrans-1,2-dichloroethylene, and about 1 to about 10 methanol; about 1 toabout 89 weight percent F22E, about 10 to about 60 weight percenttrans-1,2-dichloroethylene, and about 1 to about 85 HFC-365mfc; about 1to about 70 weight percent F22E, about 29 to about 70 weight percenttrans-1,2-dichloroethylene, and about 1 to about 70 C₄F₉OCH₃; about 1 toabout 80 weight percent F22E, about 19 to about 60 weight percenttrans-1,2-dichloroethylene, and about 1 weight percent to about Y80weight percent HFC-43-10mee; about 45 to about 85 weight percent F13iE,about 14 to about 54 weight percent trans-1,2-dichloroethylene, andabout 1 to about 10 weight percent methanol; about 1 to about 89 weightpercent F13iE, about 10 to about 60 weight percenttrans-1,2-dichloroethylene, and about 1 to about 80 weight percentHFC-43-10mee; about 1 to about 89 weight percent F13iE, about 10 toabout 60 weight percent trans-1,2-dichloroethylene, and about 1 to about84 weight percent HFC-365mfc; about 1 to about 75 weight percent F13iE,about 24 to about 70 weight percent trans-1,2-dichloroethylene, andabout 1 to about 70 weight percent C₄F₉OCH₃; about 1 to about 70 weightpercent F3i3iE, about 29 to about 95 weight percenttrans-1,2-dichloroethylene, and about 1 to about 25 weight percentmethanol; about 1 to about 65 weight percent F3i3iE, about 34 to about98 weight percent trans-1,2-dichloroethylene, and about 1 to about 15weight percent ethanol; about 1 to about 69 weight percent F3i3iE, about30 to about 70 weight percent trans-1,2-dichloroethylene, and about 1 toabout 69 weight percent C₄F₉OCH₃; about 1 to about 69 weight percentF3i3iE, about 30 to about 80 weight percent trans-1,2-dichloroethylene,and about 1 to about 69 weight percent C₄F₉OC₂H₅; about 45 to about 80weight percent F13E, about 19 to about 54 weight percenttrans-1,2-dichloroethylene, and about 1 to about 10 weight percentmethanol; about 1 to about 85 weight percent F13E, about 14 to about 60weight percent trans-1,2-dichloroethylene, and about 1 to about 80weight percent HFC-43-10mee; about 1 to about 85 weight percent F13E,about 14 to about 60 weight percent trans-1,2-dichloroethylene, andabout 1 to about 80 weight percent HFC-365mfc; about 1 to about 80weight percent F13E, about 19 to about 70 weight percenttrans-1,2-dichloroethylene, and about 1 to about 70 weight percentC₄F₉OCH₃; about 1 to about 30 weight percent F3i4E, about 25 to about 69weight percent trans-1,2-dichloroethylene, and about 30 to about 69weight percent C₄F₉OCH₃; about 1 to about 50 weight percent F3i4E, about30 to about 98 weight percent trans-1,2-dichloroethylene, and about 1 toabout 60 weight percent C₄F₉OC₂H₅; and about 1 to about 70 weightpercent F44E, about 1 to about 60 weight percenttrans-1,2-dichloroethylene, and about 29 to about 98 weight percentC₄F₉OC₂H₅.
 13. An azeotropic or azeotrope-like composition comprising anazeotropic or azeotrope-like composition selected from the groupconsisting of: 85.1 weight percent F14E and 14.9 weight percent methanolhaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 59.1° C.; 87.1 weight percent F14E and 12.9 weight percentisopropanol having a vapor pressure of about 14.7 psia (101 kPa) at atemperature of about 66.9° C.; 87.9 weight percent F14E and 12.1 weightpercent ethanol having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 65.2° C.; 44.3 weight percent F14E and 55.7weight percent trans-1,2-dichloroethylene having a vapor pressure ofabout 14.7 psia (101 kPa) at a temperature of about 44.0° C.; 54.4weight percent F14E and 45.6 weight percent n-propylbromide having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about66.6° C.; 72.1 weight percent F24E and 27.9 weight percent methanolhaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 63.4° C.; 78.1 weight percent F24E and 21.9 weight percentisopropanol having a vapor pressure of about 14.7 psia (101 kPa) at atemperature of about 74.1° C.; 79.2 weight percent F24E and 20.8 weightpercent ethanol having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 71.8° C.; 25.7 weight percent F24E and 74.3weight percent n-propylbromide having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 70.2° C.; 85.2 weight percentF24E and 14.8 weight percent perchloroethylene having a vapor pressureof about 14.7 psia (101 kPa) at a temperature of about 89.9° C.; 65.0weight percent F24E and 35.0 weight percent trichlorethylene having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about75.9° C.; 95.8 weight percent F22E and 4.2 weight percent methanolhaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 43.7° C.; 98.0 weight percent F22E and 2.0 weight percentisopropanol having a vapor pressure of about 14.7 psia (101 kPa) at atemperature of about 47.2° C.; 97.6 weight percent F22E and 2.4 weightpercent ethanol having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 46.6° C.; 71.0 weight percent F22E and 29.0weight percent trans-1,2-dichlorethylene having a vapor pressure ofabout 14.7 psia (101 kPa) at a temperature of about 33.9° C.; 87.0weight percent F22E and 13.0 weight percent n-propylbromide having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about43.3° C.; 89.8 weight percent F22E and 10.2 weight percent HFC-43-10meehaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 47.9° C.; 29.3 weight percent F22E and 70.7 weight percentHFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa) at atemperature of about 39.2° C.; 95.5 weight percent F13iE and 4.5 weightpercent methanol having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 44.4° C.; 97.8 weight percent F13iE and 2.2weight percent isopropanol having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 48.0° C.; 97.4 weight percent F13iEand 2.6 weight percent ethanol having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 47.5° C.; 70.2 weight percentF13iE and 29.8 weight percent trans-1,2-dichlorethylene having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 34.4°C.; 86.4 weight percent F13iE and 13.6 weight percent n-propylbromidehaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 44.0° C.; 95.3 weight percent F13iE and 4.7 weight percentHFC-43-10mee having a vapor pressure of about 14.7 psia (101 kPa) at atemperature of about 48.8° C.; 24.6 weight percent F13iE and 75.4 weightpercent HFC-365mfc having a vapor pressure of about 14.7 psia (101 kPa)at a temperature of about 39.5° C.; 85.0 weight percent F3i3iE and 15.0weight percent methanol having a vapor pressure of about 14.7 psia (101kPa) at a temperature of about 59.8° C.; 89.2 weight percent F3i3iE and10.8 weight percent isopropanol having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 70.0° C.; 89.0 weight percentF3i3iE and 11.0 weight percent ethanol having a vapor pressure of about14.7 psia (101 kPa) at a temperature of about 67.8° C.; 44.1 weightpercent F3i3iE and 55.9 weight percent trans-1,2-dichlorethylene havinga vapor pressure of about 14.7 psia (101 kPa) at a temperature of about44.5° C.; 22.8 weight percent F3i3iE and 77.2 weight percent C₄F₉OC₂H₅having a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 75.7° C.; 67.4 weight percent F3i3iE and 32.6 weight percentn-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 61.3° C.; 94.4 weight percent F13E and 5.6 weightpercent methanol having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 47.3° C.; 96.9 weight percent F13E and 3.1 weightpercent isopropanol having a vapor pressure of about 14.7 psia (101 kPa)at a temperature of about 51.9° C.; 96.5 weight percent F13E and 3.5weight percent ethanol having a vapor pressure of about 14.7 psia (101kPa) at a temperature of about 51.1° C.; 66.3 weight percent F13E and33.7 weight percent trans-1,2-dichloroethylene having a vapor pressureof about 14.7 psia (101 kPa) at a temperature of about 36.3° C.; 83.7weight percent F13E and 16.3 weight percent n-propylbromide having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about47.1° C.; 59.5 weight percent F13E and 40.5 weight percent HFC-43-10meehaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 52.3° C.; 7.6 weight percent F3i4E and 92.4 weight percenttrans-1,2-dichloroethylene having a vapor pressure of about 14.7 psia(101 kPa) at a temperature of about 47.6° C.; 42.8 weight percent F3i4Eand 57.2 weight percent methanol having a vapor pressure of about 14.7psia (101 kPa) at a temperature of about 65.4° C.; 57.8 weight percentF3i4E and 42.2 weight percent isopropanol having a vapor pressure ofabout 14.7 psia (101 kPa) at a temperature of about 81.0° C.; 58.7weight percent F3i4E and 41.3 weight percent ethanol having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 77.3°C.; 31.9 weight percent F3i4E and 68.1 weight percent n-propylbromidehaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 69.6° C.; 8.1 weight percent F44E and 91.9 weight percentn-propylbromide having a vapor pressure of about 14.7 psia (101 kPa) ata temperature of about 70.9° C.; 34.4 weight percent F14E, 59.0 weightpercent trans-1,2-dichloroethyene, and 6.6 weight percent methanolhaving a vapor pressure of about 14.7 psia (101 kPa) at a temperature ofabout 39.9° C.; 41.9 weight percent F14E, 55.1 weight percenttrans-1,2-dichloroethyene, and 3.0 weight percent ethanol having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 43.2°C.; 10.3 weight percent F24E, 80.3 weight percenttrans-1,2-dichloroethyene, and 9.4 weight percent methanol having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about41.0° C.; 24.8 weight percent F24E, 70.9 weight percenttrans-1,2-dichloroethyene, and 4.3 weight percent ethanol having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 43.0°C.; 67.9 weight percent F22E, 29.7 weight percenttrans-1,2-dichloroethyene, and 2.4 weight percent methanol having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about32.6° C.; 45.4 weight percent F22E, 27.2 weight percenttrans-1,2-dichloroethyene, and 27.4 weight percent HFC-365mfc having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about33.0° C.; 66.9 weight percent F13iE, 30.6 weight percenttrans-1,2-dichloroethyene, and 2.5 weight percent methanol having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about33.0° C.; 69.8 weight percent F13iE, 29.8 weight percenttrans-1,2-dichloroethyene, and 0.4 weight percent HFC-43-10mee having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about34.4° C.; 41.9 weight percent F13iE, 27.8 weight percenttrans-1,2-dichloroethyene, and 30.3 weight percent HFC-365mfc having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about33.3° C.; 32.9 weight percent F3i3iE, 60.2 weight percenttrans-1,2-dichloroethyene, and 6.9 weight percent methanol having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about40.1° C.; 41.1 weight percent F3i3iE, 56.3 weight percenttrans-1,2-dichloroethyene, and 2.6 weight percent ethanol having a vaporpressure of about 14.7 psia (101 kPa) at a temperature of about 43.8°C.; 62.2 weight percent F13E, 34.7 weight percenttrans-1,2-dichloroethyene, and 3.1 weight percent methanol having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about34.5° C.; 48.0 weight percent F13E, 33.2 weight percenttrans-1,2-dichloroethyene, and 18.8 weight percent HFC-43-10mee having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about36.1° C.; 23.1 weight percent F13E, 30.3 weight percenttrans-1,2-dichloroethyene, and 46.6 weight percent HFC-365mfc having avapor pressure of about 14.7 psia (101 kPa) at a temperature of about34.4° C.;
 14. A composition consisting essentially of the azeotrope-likecomposition of claim 12 and an aerosol propellant.
 15. The compositionof claim 14, wherein the aerosol propellant is selected from the groupconsisting of air, nitrogen, carbon dioxide, difluoromethane,trifluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane,pentafluoroethane, heptafluoropropane, and pentafluoropropane.
 16. Acomposition comprising the azeotropic composition of claim 13 and anaerosol propellant.
 17. The composition of claim 16, wherein the aerosolpropellant is selected from the group consisting of air, nitrogen,carbon dioxide, difluoromethane, trifluoromethane, difluoroethane,trifluoroethane, tetrafluoroethane, pentafluoroethane,heptafluoropropane, and pentafluoropropane.
 18. A process for cleaning,comprising: a. contacting a surface comprising a residue with thecomposition of claim 12 and b. recovering the surface from thecomposition.
 19. The process of claim 18 wherein said residue comprisesan oil.
 20. The process of claim 18 wherein said residue comprises arosin flux.
 21. The process of claim 18 wherein said surface is anintegrated circuit device.
 22. A process for cleaning, comprising: a.contacting a surface comprising a residue with the composition of claim13 and b. recovering the surface from the composition.
 23. The processof claim 22 wherein said residue comprises an oil.
 24. The process ofclaim 22 wherein said residue comprises a rosin flux.
 25. The process ofclaim 22 wherein said surface is an integrated circuit device.